CN104107689A - Macroporous nanocomposite and preparation method thereof - Google Patents
Macroporous nanocomposite and preparation method thereof Download PDFInfo
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- CN104107689A CN104107689A CN201310135715.3A CN201310135715A CN104107689A CN 104107689 A CN104107689 A CN 104107689A CN 201310135715 A CN201310135715 A CN 201310135715A CN 104107689 A CN104107689 A CN 104107689A
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Abstract
The invention relates to a macroporous nanocomposite and a preparation method thereof. The macroporous nanocomposite is characterized by being composed of a macroporous three-dimensional SiO2 ultrathin film substrate and zinc oxide nanowires which distribute in three-dimensional channels in the three-dimensional SiO2 ultrathin film substrate, wherein the zinc oxide nanowires account for 30-50 wt% of the macroporous nanocomposite. The preparation method includes following steps: preparing a three-dimensional skeleton structure from epoxy resin; soaking the three-dimensional skeleton structure in tetraethyl orthosilicate; performing a calcination process in a muffle furnace to obtain a three-dimensional SiO2 ultrathin film; then introducing nano zinc oxide crystal seeds through combination of a conventional sol-gel method; immerging the three-dimensional SiO2 ultrathin film into a zinc-ammonia complex aqueous solution as an impregnating solution; and finally generating the zinc oxide nanowires in the three-dimensional channels through a stepwise hydrothermal process. The macroporous nanocomposite can not only be used as a photocatalyst but also be used as a carrier material for carrying a biocatalyst - an enzyme. The macroporous nanocomposite is suitable for an industrial application.
Description
Technical field
The present invention relates to nano material complex technique field, particularly a kind of zinc oxide nanowire is grown in to resulting nano composite material and preparation method thereof in large scale, large aperture silica.
Background technology
ZnO nano-wire (monodimension nanometer material) is a kind of novel nano material, in the performances such as optics, electronic transport, photoelectricity, piezoelectricity, power electricity, a transmitting, rare magnetic, photocatalysis, suction ripple, there is distinguishing feature, in fields such as sensing optics, electronics, a transmitting, piezoelectricity, the energy, catalysis, demonstrated good application prospect.
Making ZnO nano wire has several different methods, there is solwution method, molecular beam epitaxy, pulsed laser deposition, metal-organic chemical vapor deposition equipment etc., as mono-kind of the patent No. Chinese invention patent < < that is CN200710037758.2 is grown in graphical ZnO nano thread structure in glass substrate and preparation method thereof > >, this structure is attached in glass substrate, the ZnO nano-wire that is periodic pattern, the diameter of nano wire and length are respectively 50～100nm and 0.5～1 μ m, the nanowire length in each cycle is 400 μ m.This structure is under the condition of lower temperature and normal pressure, by thermal evaporation technique by ZnO the periodicity cavity of the template in cavity periodically of the band by covering glass substrate surface, be grown on glass substrate surface.It is to using electro-conductive glass as substrate, adopts the technique of thermal evaporation to be prepared.
Hydrothermal synthesis method, it refers under certain temperature and pressure condition, utilizes the chemical reaction of material in the aqueous solution to prepare the method for nano material, under hydrothermal condition, water can be used as a kind of chemical constituent and works and participate in reaction, is solvent and mineralizer.The existing patent No. is the method > > of the China invention < < hydrothermal reaction at low temperature synthesizing zinc oxide nano tube array of CN200810153801.6, step is: (1) making ZnO crystal seed layer, (2) low-temperature hydrothermal growing ZnO nano-wire, (3) ZnO nano-wire chemical etching becomes ZnO nano pipe; It is to adopt hydrothermal reaction at low temperature, utilize pure chemistry etching technics to synthesize ZnO nano pipe array, do not need electrochemistry to assist and template, by controlling the etch period of concentration, hydrothermal growth time and the alkali lye of reactant, can on dissimilar matrix, prepare the controlled ZnO nano pipe of caliber size; Have cost low, reaction temperature is low, directly in the aqueous solution, carries out, and does not produce poisonous and harmful refuse, and with short production cycle, rate of return on investment is high.
The present invention is applied to a kind of large pore material by hydrothermal synthesis method, the place using large pore material itself as synthetic reaction, thereby the ZnO nano-wire generating just can be compound with large pore material, forms new composite.
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of large aperture nano composite material, take large aperture silica as template, has the performance that ZnO nano-wire has concurrently, and size, shape is adjustable, can directly as carrier or photochemical catalyst, use.
Second technical problem to be solved by this invention is to provide the preparation method of a kind of large aperture nano composite material, take large aperture silica as template, adopt hydrothermal synthesis method that the ZnO nano-wire and the large pore material that generate is compound, form new composite, the composite size, the shape that make are adjustable, have the performance that ZnO nano-wire has concurrently, can directly as carrier or photochemical catalyst, use.
The present invention solves the technical scheme that above-mentioned first technical problem adopts: a kind of large aperture nano composite material, is characterized in that: this large aperture nano composite material is by wide-aperture D S iO
2ultrathin membrane matrix and be distributed in D S iO
2zinc oxide nanowire in the 3 D pore canal of ultrathin membrane matrix forms, and wherein zinc oxide nanowire content is 30～50Wt.% of large aperture nano composite material.
As improvement, described D S iO
2the thickness of ultrathin membrane matrix is 20～50nm, and porosity is 80%～95%, and specific area is 100～140m
2g
-1, the diameter of described zinc oxide nanowire is 10～20nm, and length is 500～1000nm, and the specific area of described large aperture nano composite material is 120～170m
2g
-1.
Finally, described zinc oxide nanowire is linear pattern or flexure type.
The present invention solves the technical scheme that above-mentioned second technical problem adopt: the preparation method of a kind of large aperture nano composite material, is characterized in that comprising the following steps:
1) preparation of three-dimensional framework polymer template: the epoxy resin that is 1:4～1:2 by mass ratio and polyethylene glycol mix and be heated to 50～70 ℃, stir and within 5～15 minutes, become after clear solution, the polyamines liquid that to add rapidly with epoxy resin mass ratio be 1:2～1:10, after stirring, pour in polytetrafluoroethylene (PTFE) mould and shape, keep setting temperature in 50～70 ℃, after 1～2 hour, to form the solid shaped polymer blend of white, with pure water immersion, after 10～20 hours, remove polyethylene glycol phase completely, leave the epoxy resin of three-dimensional framework structure, at room temperature natural drying 1～5 day,
2) D S iO
2the preparation of ultrathin membrane matrix: the epoxy resin of the three-dimensional framework structure that step 1) is made soaks 1～5 hour in the mixed liquor of cyclohexane and tetraethyl orthosilicate, forms SiO after exposing 10～20 hours in ammoniacal liquor atmosphere in 25～35 ℃
2/ epoxy resin composite, within dry 1～5 hour, to remove the ethanol of generation and the ammoniacal liquor of absorption, the heating rate with 10～20 ℃/min in Muffle furnace rises to 600～900 ℃, keeps can obtaining D S iO in 10～60 minutes
2ultrathin membrane matrix;
3) introducing of zinc oxide crystal seed: the Zn that is 1:2～1:6 by mass ratio (Ac)
22H
2o and polyethylene glycol are dissolved in wiring solution-forming in water, by above-mentioned D S iO
2ultrathin membrane matrix is dipped in solution and places 1.5～2.5 hours, after taking-up, in the baking oven of 80～120 ℃, dry 1～3 hour, then at 2.5～3.5 hours, be evenly raised to 650 ℃ from 200 ℃ gradually sample being put into Muffle furnace, zinc oxide crystal seed evenly can be introduced;
4) growth of zinc oxide nanowire: by Zn (NO
3)
26H
2o reacts with excessive concentrated ammonia liquor, being made into concentration is the zinc ammonia complex aqueous solution of the clarification of 0.9～1.1mol/L, the silica large pore material of above-mentioned introducing crystal seed is dipped in solution and is placed 1.5～2.5 hours, then solid sample is put in the reaction vessel of sealing, reaction vessel is placed some silica gel that soak persulfate solution in advance, solid sample and silica gel isolation, set temperature is 80～90 ℃, temperature retention time is 10～14 hours, by gas phase diffusion, make ammonia gradually by the sulfuric acid absorption on silica gel, complex in large pore material changes into zinc hydroxide again, and uniform deposition is on hole wall, the temperature of reaction vessel is elevated to 95～105 ℃, continue insulation 20～28 hours, on crystal seed, grow zinc oxide nanowire.
The chemical reaction of said process can be expressed as:
[Zn(NH
3)
4](OH)
2→Zn(OH)
2+4NH
3↑
Zn (OH)
2→ ZnO(nano wire)+H
2o
As preferably, the mass ratio of described cyclohexane and tetraethyl orthosilicate is 1:3～3:1.
As preferably, described Zn (Ac)
22H
2the mass ratio of O and polyethylene glycol is 1:3～1:6.
Preferred again, described polyethylene glycol is that molecular weight is one or both in 600,1000 or 2000.
Improve again described D S iO
2the thickness of ultrathin membrane matrix is 20～50nm, and porosity is 80%～95%, and specific area is 100～140m
2g
-1, can be by repeating step 2) and to increase D S iO
2the thickness of ultrathin membrane or dilute tetraethyl orthosilicate by cyclohexane and reduce D S iO
2the thickness of ultrathin membrane.
Finally, the diameter of described zinc oxide nanowire is 10～20nm, and length is 500～1000nm, and the specific area of described large aperture nano composite material is 120～170m
2g
-1, can be by repeating step 4) and to increase the length of zinc oxide nanowire.Epoxy resin adopts the resin of trade mark E-44.
Compared with prior art, the invention has the advantages that: using large aperture silica as template, adopt hydrothermal synthesis method that the ZnO nano-wire and the large pore material that generate is compound, form new composite, the composite size, the shape that make are adjustable, are convenient to make large-sized material; Nano wire in macroporous silica is easily controlled than simple nano wire, the nano wire that large pore material also can be wherein provides natural protection, makes its mechanical damage of avoiding external force, maintains its primary morphology, stop it and associate mutually, avoid it to be subject to environment dust pollution; Large pore material after compound has higher surface area, stronger absorption property, and there is the intrinsic semiconducting behavior of nano zine oxide, can carry out the application such as photocatalysis; The nano wire of growing in 3 D pore canal is than thinner under usual terms, and its diameter is generally no more than 20nm, so its specific area is larger; Nano wire is grown and is had the productive rate than higher under usual terms in 3 D pore canal, can approach 100%, and composite of the present invention both can be used as photochemical catalyst, can be used as again carrier material for load biocatalyst--enzyme, is applicable to the needs of industrial use.
Accompanying drawing explanation
Fig. 1 is the electron-microscope scanning figure of the three-dimensional framework polymer of the embodiment of the present invention 1;
Fig. 2 is the electron-microscope scanning figure of the SiO2 large pore material of the embodiment of the present invention 1;
Fig. 3 is the electron-microscope scanning figure of a zinc-oxide nano ball of string for the embodiment of the present invention 1;
Fig. 4 is the electron-microscope scanning figure of the zinc oxide nanowire cage of the embodiment of the present invention 1;
Fig. 5 .1,5.2 is the electron-microscope scanning figure of the zinc oxide nanowire bunch of the embodiment of the present invention 1.
The specific embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention.
Embodiment 1
Step 1: the preparation of three-dimensional framework polymer template, the epoxy resin that is 1:2 by mass ratio (trade mark E-44) and polyethylene glycol mix and are heated to 60 ℃, stir and within 10 minutes, become after clear solution, the triethylene tetramine that to add rapidly with epoxy resin mass ratio be 1:6, after stirring, pour in polytetrafluoroethylene (PTFE) mould and shape, keep setting temperature in 70 ℃, after 2 hours, to form the solid shaped polymer blend of white, with pure water immersion, after 15 hours, remove polyethylene glycol phase completely, leave the epoxy resin (see figure 1) of three-dimensional framework structure, at room temperature natural drying 3 days,
The molecular weight of polyethylene glycol is 1000.
Step 2:SiO
2the preparation of large pore material, the epoxy resin that is about to three-dimensional framework structure in step 1 soaks 2 hours in cyclohexane and tetraethyl orthosilicate mixed liquor (volume ratio 1:3), forms SiO after exposing 15 hours in ammoniacal liquor atmosphere in 30 ℃
2/ epoxy resin composite, within dry 2 hours, to remove the ethanol of generation and the ammoniacal liquor of absorption, the heating rate with 20 ℃/min in Muffle furnace rises to 800 ℃, keeps can obtaining SiO in 20 minutes
2large pore material (see figure 2), the thickness of silica substrate is 50nm, and porosity is 80%, and specific area is 100m
2g
-1.
Step 3: the introducing of zinc oxide crystal seed: the Zn that is 1:6 by mass ratio (Ac)
22H
2o and Macrogol 600 are dissolved in wiring solution-forming in water, Zn
2+concentration be 0.25mol/L.By above-mentioned SiO
2ultrathin membrane is dipped in solution and places 2 hours, after taking-up, dries 1～3 hour in the baking oven of 80～120 ℃, then at 3 hours, is evenly raised to 650 ℃ from 200 ℃ gradually sample being put into Muffle furnace, zinc oxide crystal seed evenly can be introduced.
Step 4: the growth of zinc oxide nanowire: by Zn (NO
3)
26H
2o reacts with excessive concentrated ammonia liquor, being made into concentration is the zinc ammonia complex solution of the clarification of 1mol/L, the silica large pore material of above-mentioned introducing crystal seed is dipped in solution and is placed 2 hours, then solid sample is put in the reaction vessel of sealing, reaction vessel is placed some silica gel that soak persulfate solution in advance, solid sample and silica gel isolation, set temperature is 90 ℃, temperature retention time is 12 hours, again the temperature of reaction vessel is elevated to 100 ℃, continue insulation 24 little, in this process, zinc hydroxide dissolves gradually, in duct, bear zinc oxide nanowire (see figure 3).The diameter of zinc oxide nanowire is 10～20nm, and length is 1-2 μ m, and the specific area of composite is 126m
2/ g.
Embodiment 2
Step 1: the preparation of three-dimensional framework polymer template, the epoxy resin that is 1:2 by mass ratio (trade mark E-44) and polyethylene glycol mix and are heated to 60 ℃, stir and within 10 minutes, become after clear solution, the triethylene tetramine that to add rapidly with epoxy resin mass ratio be 1:6, after stirring, pour in polytetrafluoroethylene (PTFE) mould and shape, keep setting temperature in 70 ℃, after 2 hours, to form the solid shaped polymer blend of white, with pure water immersion, after 15 hours, remove polyethylene glycol phase completely, leave the epoxy resin of three-dimensional framework structure, at room temperature natural drying 3 days;
The molecular weight of polyethylene glycol is 1000.
Step 2:SiO
2the preparation of large pore material, the epoxy resin that is about to three-dimensional framework structure in step 1 soaks 2 hours in cyclohexane and tetraethyl orthosilicate mixed liquor (volume ratio 1:1), forms SiO after exposing 15 hours in ammoniacal liquor atmosphere in 30 ℃
2/ epoxy resin composite, within dry 2 hours, to remove the ethanol of generation and the ammoniacal liquor of absorption, the heating rate with 20 ℃/min in Muffle furnace rises to 800 ℃, keeps can obtaining SiO in 20 minutes
2large pore material, the thickness of silica substrate is 30nm, and porosity is 88%, and specific area is 123m
2g
-1.
Step 3: the introducing of zinc oxide crystal seed: the Zn that is 1:3 by mass ratio (Ac)
22H
2o and Macrogol 600 are dissolved in wiring solution-forming in water, Zn
2+concentration be 0.25mol/L.By above-mentioned SiO
2ultrathin membrane is dipped in solution and places 2 hours, after taking-up, dries 1～3 hour in the baking oven of 80～120 ℃, then at 3 hours, is evenly raised to 650 ℃ from 200 ℃ gradually sample being put into Muffle furnace, zinc oxide crystal seed evenly can be introduced.
Step 4: the growth of zinc oxide nanowire: by Zn (NO
3)
26H
2o reacts with excessive concentrated ammonia liquor, being made into concentration is the zinc ammonia complex solution of the clarification of 1mol/L, the silica large pore material of above-mentioned introducing crystal seed is dipped in solution and is placed 2 hours, then solid sample is put in the reaction vessel of sealing, reaction vessel is placed some silica gel that soak persulfate solution in advance, solid sample and silica gel isolation, set temperature is 90 ℃, temperature retention time is 12 hours, again the temperature of reaction vessel is elevated to 100 ℃, continue insulation 24 little, in this process, zinc hydroxide dissolves gradually, in duct, grow zinc-oxide nano ball of string (see figure 4).The diameter of zinc oxide nanowire is 10～20nm, and length is 2～5 μ m, and the specific area of composite is 143m
2/ g.
Embodiment 3
Step 1: the preparation of three-dimensional framework polymer template, the epoxy resin that is 1:2 by mass ratio (trade mark E-44) and polyethylene glycol mix and are heated to 60 ℃, stir and within 10 minutes, become after clear solution, the triethylene tetramine that to add rapidly with epoxy resin mass ratio be 1:6, after stirring, pour in polytetrafluoroethylene (PTFE) mould and shape, keep setting temperature in 70 ℃, after 2 hours, to form the solid shaped polymer blend of white, with pure water immersion, after 15 hours, remove polyethylene glycol phase completely, leave the epoxy resin of three-dimensional framework structure, at room temperature natural drying 3 days;
The molecular weight of polyethylene glycol is 2000.
Step 2:SiO
2the preparation of large pore material, the epoxy resin that is about to three-dimensional framework structure in step 1 soaks 2 hours in cyclohexane and tetraethyl orthosilicate mixed liquor (volume ratio 3:1), forms SiO after exposing 15 hours in ammoniacal liquor atmosphere in 30 ℃
2/ epoxy resin composite, within dry 2 hours, to remove the ethanol of generation and the ammoniacal liquor of absorption, the heating rate with 20 ℃/min in Muffle furnace rises to 800 ℃, keeps can obtaining SiO in 20 minutes
2large pore material, the thickness of silica substrate is 20nm, and porosity is 95%, and specific area is 140m
2g
-1.
Step 3: the introducing of zinc oxide crystal seed: the Zn that is 1:3 by mass ratio (Ac)
22H
2o and Macrogol 600 are dissolved in wiring solution-forming in water, Zn
2+concentration be 0.1mol/L.By above-mentioned SiO
2ultrathin membrane is dipped in solution and places 2 hours, after taking-up, dries 1～3 hour in the baking oven of 80～120 ℃, then at 3 hours, is evenly raised to 650 ℃ from 200 ℃ gradually sample being put into Muffle furnace, zinc oxide crystal seed evenly can be introduced.
Step 4: the growth of zinc oxide nanowire: by Zn (NO
3)
26H
2o reacts with excessive concentrated ammonia liquor, being made into concentration is the zinc ammonia complex solution of the clarification of 1mol/L, the silica large pore material of above-mentioned introducing crystal seed is dipped in solution and is placed 2 hours, then solid sample is put in the reaction vessel of sealing, reaction vessel is placed some silica gel that soak persulfate solution in advance, solid sample and silica gel isolation, set temperature is 80 ℃, temperature retention time is 12 hours, again the temperature of reaction vessel is elevated to 100 ℃, continue insulation 24 little, this step repeats after 2 times, in duct, grow the zinc oxide nanowire (see figure 5) that bunch shape arrives, the diameter of zinc oxide nanowire is 10～20nm, length is 0.5～1 μ m, the specific area of composite is 168m
2/ g.
The load capacity of ZnO nano-wire is definite by the method weighing, and the gross weight of composite deducts the weight of carrier.
The pattern scanning electron microscope analysis of composite.
Adopt JW-K type specific area and pore-size distribution tester (precise and tiny Gao Bo, Beijing science and technology Co., Ltd) to analyze the specific area of sample, first sample is heated to 150 ℃ and maintain 4h to remove the material of sample absorption under vacuum, then under 77K, measure, with BET formula, calculate its specific area.
The present invention is applied to large pore material by hydrothermal synthesis method, the place using large pore material itself as synthetic reaction, thereby the ZnO nano-wire generating just can be compound with large pore material, forms new composite.The large pore material that we use is the silica with three-dimensional superthin structure, unformed silica nanometer thickness of thin layer is adjustable in 20-50nm scope, the mode of extending by three-dimensional bending forms macroscopic body, and its pore size is 1 micron of left and right, and porosity is large, apparent density is little, specific area is high, the good mechanical stability of material, large scale flawless, duct is three-dimensional to be connected, and does not have dead hole, thereby permeability for liquids is very strong, is suitable as very much reacting environment.Nano wire restrained in 3 D pore canal is all easily controlled than simple nano wire in reality use or scientific research; the nano wire that large pore material also can be wherein provides natural protection; make it avoid the mechanical damage of external force; maintain its primary morphology; stopping it associates mutually; avoid it to be subject to environment dust pollution, the performance (as absorption property, catalytic performance etc.) that ZnO nano-wire has simultaneously can be embodied in new composite.
Claims (9)
1. a large aperture nano composite material, is characterized in that: this large aperture nano composite material is by wide-aperture D S iO
2ultrathin membrane matrix and be distributed in D S iO
2zinc oxide nanowire in the 3 D pore canal of ultrathin membrane matrix forms, and wherein zinc oxide nanowire content is 30～50Wt% of large aperture nano composite material.
2. large aperture according to claim 1 nano composite material, is characterized in that described D S iO
2the thickness of ultrathin membrane matrix is 20～50nm, and porosity is 80%～95%, and specific area is 100～140m
2g
-1, the diameter of described zinc oxide nanowire is 10～20nm, and length is 0.5～5 μ m, and the specific area of described large aperture nano composite material is 120～170m
2g
-1.
3. large aperture according to claim 1 and 2 nano composite material, is characterized in that described zinc oxide nanowire is linear pattern or flexure type.
4. a preparation method for large aperture nano composite material, is characterized in that comprising the following steps:
1) preparation of three-dimensional framework polymer template: the epoxy resin that is 1:4～1:2 by mass ratio and polyethylene glycol mix and be heated to 50～70 ℃, stir and within 5～15 minutes, become after clear solution, the polyamines liquid that to add rapidly with epoxy resin mass ratio be 1:2～1:10, after stirring, pour in polytetrafluoroethylene (PTFE) mould and shape, keep setting temperature in 50～70 ℃, after 1～2 hour, to form the solid shaped polymer blend of white, with pure water immersion, after 10～20 hours, remove polyethylene glycol phase completely, leave the epoxy resin of three-dimensional framework structure, at room temperature natural drying 1～5 day,
2) D S iO
2the preparation of ultrathin membrane matrix: the epoxy resin of the three-dimensional framework structure that step 1) is made soaks 1～5 hour in tetraethyl orthosilicate, forms SiO after exposing 10～20 hours in ammoniacal liquor atmosphere in 25～35 ℃
2/ epoxy resin composite, within dry 1～5 hour, to remove the ethanol of generation and the ammoniacal liquor of absorption, the heating rate with 10～20 ℃/min in Muffle furnace rises to 600～900 ℃, keeps can obtaining D S iO in 10～60 minutes
2ultrathin membrane matrix;
3) introducing of zinc oxide crystal seed: the Zn that is 1:2～1:6 by mass ratio (Ac)
22H
2o and polyethylene glycol are dissolved in wiring solution-forming in water, by above-mentioned D S iO
2ultrathin membrane matrix is dipped in solution and places 1.5～2.5 hours, after taking-up, in the baking oven of 80～120 ℃, dry 1～3 hour, then at 2.5～3.5 hours, be evenly raised to 650 ℃ from 200 ℃ gradually sample being put into Muffle furnace, zinc oxide crystal seed evenly can be introduced;
4) growth of zinc oxide nanowire: by Zn (NO
3)
26H
2o reacts with excessive concentrated ammonia liquor, being made into concentration is the zinc ammonia complex aqueous solution of the clarification of 0.9～1.1mol/L, the silica large pore material of above-mentioned introducing crystal seed is dipped in solution and is placed 1.5～2.5 hours, then solid sample is put in the reaction vessel of sealing, reaction vessel is placed some silica gel that soak persulfate solution in advance, solid sample and silica gel isolation, set temperature is 80～90 ℃, temperature retention time is 10～14 hours, by gas phase diffusion, make ammonia gradually by the sulfuric acid absorption on silica gel, complex in large pore material changes into zinc hydroxide again, and uniform deposition is on hole wall, the temperature of reaction vessel is elevated to 95～105 ℃, continue insulation 20～28 hours, on crystal seed, grow zinc oxide nanowire.
5. preparation method according to claim 4, the mass ratio that it is characterized in that described cyclohexane and tetraethyl orthosilicate is 1:3～3:1.
6. preparation method according to claim 4, is characterized in that described Zn (Ac)
22H
2the mass ratio of O and polyethylene glycol is 1:3～1:6.
7. preparation method according to claim 4, is characterized in that: the molecular weight of described polyethylene glycol is one or both in 600,1000 or 2000.
8. preparation method according to claim 4, is characterized in that: described D S iO
2the thickness of ultrathin membrane matrix is 20～50nm, and porosity is 80%～95%, and specific area is 100～140m
2g
-1.
9. preparation method according to claim 4, is characterized in that: the diameter of described zinc oxide nanowire is 10～20nm, and length is 500～1000nm, and the specific area of described large aperture nano composite material is 120～170m
2g
-1.
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| CN104628411B (en) * | 2015-02-05 | 2020-02-11 | 宁波大学 | Super-macroporous material loaded with copper oxide nanowires |
| CN108940228A (en) * | 2017-05-19 | 2018-12-07 | 宁波大学 | A kind of Polymer adsorption material and preparation method thereof that can remove particulate in air matter |
| CN108940363A (en) * | 2017-05-19 | 2018-12-07 | 宁波大学 | A kind of macroporous/mesoporous composite photocatalyst and preparation method thereof |
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